Oxyalkylated amine-modified thermoplastic phenol-aldehyde resins, and method of making same



OXYALKYLATED AMINE-MODIFIED THERMO- PLASTIC PHENOL-ALDEHYDE RESINS, AND METHOD or MAKING SAME Melvin De Groote, University City, Mo., assignor to Petrolite Corporation, Wilmington, Del., a corporation of Delaware No Drawing. Application July 30, 1952, Serial No. 301,806

8 Claims (Cl. 260-45) The present application is a continuation-in-part of my co-pending application, Serial No. 288,745, filed May 19, 1952. The present invention is concerned with derivatives obtained by the oxyalkylation, particularly the oxyethylation or oxypropylation of certain resin condensates.

These resin condensates are described in detail in the aforementioned co-pending application, Serial No. 288,- 745, and are obtained by the process of condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenolaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of theformula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical, and any substituted tetrahydropyrimidine radical; and formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylanon-susceptible.

Compounds or derivatives are obtained by the process of oxyalkylating said amine-modified resin condensates by a member selected from the class of ethylene oxide, propylene oxide, butylene oxide, glycide and methylgly cide. One aspect of the invention is, of course, the procedure for obtaining such oxyalkylation products.

In many instances and for various purposes, particularly for the resolution of petroleum emulsions of the waterin-oil type, one may combine a comparatively large proportion of the alkylene oxide, particularly propylene oxide or a combination of propylene oxide and ethylene oxide, with a comparatively small proportion of the resin condensa'te. In some instances the ratio by weight has been as high as SO-to-l, i. e., the ultimate product of reaction contained approximately 2% of resin condensate and approximately 98% of alkylene oxide.

reactants are concerned which are-subjected to oxyalkylation are certain amine-modified thermoplastic phenol- This invention in a more limited aspect as far as thealdehyde resins. Such amine-modified resins are described in the aforementioned co-pending application and much that is said herein is identical with the text of said aforementioned co-pending application. For purpose of simplicity the invention, purely from a standpoint of the resin condensate involved, may be exemplified by an idealized formula as follows:

i in which R represents an aliphatic hydrocarbon substituent generally having four and not over 18 carbon atoms but most preferably not over 14 carbon atoms, and It generally is a small whole number varying from 1 to 4. In the resin structure it is shown as being derived from formaldehyde although obviously other aldehydes are equally satis-- in which R represents any appropriate carbon-linked radical, such as an alkyl, alicyclic, arylalkyl radical, etc., with the proviso that at least one occurrence of R contains an amino radical which is not part of a primary amino radical or part of a substituted imidazoline radical or part of a substituted tetrahydropyrimidine radical, and with the further proviso that there be present at least one hydroxylated hydrocarbon radical such as a hydroxyl alkyl radical, a hydroxy alicyclic radical, a hydroxy alkylaryl radical, etc. The "term carbonalinked radical. is intended to. mean a radical attached to the nitrogen atom of the above formula by a bond from a carbon atom. Such hydroxylated radical need not be limited to a single hydroxyl.

group as in the case of an alkanol radical but may include 2 or more hydroxyl groups, such as a glycerol derivativev in which R' has its prior significance, R represents a hydrogen atom or radical R, D is a hydrogen atom oran alkyl group, n represents the numerals 1 to 10, and x represents a small whole number varying from 1 to 7 but; generally from 1 to 3, with the proviso that the other previously stated requirements are met. See U. S. Patent No. 2,250,176, dated July 22, 1941, to Blair. Reaction with an alkylene oxide, such as ethylene oxide or propylene oxide must of course be sure that the derivative so obtained still has-at least one secondary amino hydrogen group, all of-which will be illustrated by numerous examples subsequently.

See also U. S. Patent No. 2,362,464, dated November 14,1944, to 'Britton et al.,"which describes alkyleneidiamines and polymethylene diamines having the formula where R-representsan alkyl, "alkenyl, cycloalkyl, or aralkyl radical; andn represents, a comparatively small integer such as 1 to 8. Suchcompoundias thetone just described can be reacted with a single mole of ethylene oxide or propylene oxide orglycide to give'a suitable reactant.

A further limitation in light of the required basicity is thatthe. secondary amino radical .shallnot be directly joined .to an aryl radicaLor. acyl radical. or some other negative .radical. Needless to say, what hasbeen stated above in regard to the groups attached .tonitrogen is not intended toexclude an oxygen-interrupted carbon atom linkage. or a ringlinkageas in the instance of compounds obtained by converting an -N.-aminoalkylmorpholine of the .formula The introduction of 'two' suchhydroxylated p'olyarnine radicals into a comparatively'sm'all resin-molecule, for instance, one having'3 to 6 phenolic-nuclei asspecified,

alters thepr'oduct ina'number of'ways. In the first place, a basic-nitrogen atom," of course, adds ahydrophile effect; "in the secondp'lace, depending onthesize' of th'e rzidic'aFR, there may be 'a counter balancing"hydrophobc efiect or one in which the hydrophobeetfectmore than counterbalances the hydrophileefiect of'the nitrogen,

atom. "Finally, in suchcaseswhere"R""contains' one or more oxygen atomsyanothe'reffect is introduced, particularly another hydropliileeffect. In the present'procedurethe polyamine reactant invariably has at least one hydroxyl group and also may have a'reoccurring ether linkage, 'a'lFof'Which'in turn'afrects'the hydrophile properties.

I am not aware that it has been previously suggested to modify resins of'the kind herein described by oxyalkylation, such as oxyethylation or oxypropylation.

Referring again to the resins as such, it i's'worth noting that combinations, either resinous or otherwise, have been prepared" from phenols, aldehydes, and reactive amines particularly monoanu'nes.

Combinations, resinous or otherwise, have been -prepared from phenols, aldehydes, andwre'active amines, particularly-amines having secondaryamino groups. Generally speaking, such materials -have fallen-'dnto-three classes; the first represents non-resinous combinations derivdfrom' phenols assu'ch; the second class"represents have at least three points of reaction, per

resins which are usually insoluble and used for the purpose-for which ordinary resins, particularly thermo-setting resins are adapted. The third class represents resins which are soluble as initially prepared but are not heat-stable, i. e., they are heat-convertible, which means they are not particularly suited as raw' materials for subsequent chemical reaction which. requires temperatures above the boiling. point of water or thereabouts.

As to the preparation .ofithe ifirst class, i. e.,--nonresinous materials obtained from phenols, aldehydes and amines, particularly secondary: amines, see UnitedfStates Patents Nos. 2,218,739, dated October 22, 1940, to Bruson; 2,033,092, dated March 3, 1936, to Bruson; and

' 2,036,916, dated April'7, 1936,-to'Bruson.

As to a procedure by which aresin is produced as such involving all three reactants vand'generally resulting in an insoluble resin, or in any event, a resin which be comes insoluble in presence of added. formaldehyde .or the'like, see United StatesPatents Nos-2,341,907, dated February 15, 1944, to Cheetham et al.;2,l22,433, dated July 5, 1938, to'Meigs;2,168',335,dated August" 8,. 1939, to Heckert; 2,098,869, dated November 9, 1937, to Harmon" et' al.; and. 2,211,960, dated August 20, 19 40, toM'eigs.

'A'third' class" of material which approaches the closest to the herein-described derivatives or resinous. amino "derivatives'is described in US. 'Patent'No. 2,031,557,jdated February 18, 1936, to Bruson. The procedure described in 'said'Bruson patent apparently is concerned with the use of monoamine only.

"The resins employed as raw materials .in the instant procedure are 'characteri'zedby thepresence' of an aliphatie radical in the'ortho or'para'position, i.-e., the phenols themselves are difunctional phenols. "This is a. ditlferentiation'from the resins described in the aforementioned Br-uson Patent No. 2,03 l ,557, insofarthat said patent discloses suitable resins'obtained' from meta-substituted phenols, hydroxybenzene, resorcinol, p,p(dihydroxydiphenyl)-dimethylmethane,-and the like, all of which phenolic nuclei and as a result can yield resinswhich may be at least incipiently cross-linked even though they are apparently still soluble inoxygenated organic solvent or else are heatreactive 'insofar that they. may approach-insolubilityt or become insoluble due to the effect of'-heat,- or iadded formaldehyde,. or both.

'Theresins herein employed contain only two terminal groups whichrarenreactive to formaldehyde, i.- e., they are difunctional from .the standpoint of methylol-forming reactions. As is well known, althoughone maystart with difunctional,phenols, and. depending on the procedure emp1oyed,.,one. may obtain cross-.linking'whichi indicates that'rone or more 0f:the phenolic nuclei .have' been converted from a. difunctional radical :to. a trifunctional. radical, 0min :termsof the resin,--the moleculeeasa whole has a methylol-forming reactivity, greater than 2. Such shift can take place after the resin has been formedrorlduring resin formation. Briefly, an example is simply where an alkyl radical, such as methyl, ethyl, propyl, butyl, or. the like, shifts .from an ortho positionv to a meta position, or from-apara; positionto a metaposition. For instance, in-.the case-ofphenol-aldehyde' varnish resins, one can prepare at-leastsomein-which the resins,- insteadof having. only two points of reaction can have.three,=and; possibly more, points of reaction, with formaldehyde, or any other reactantwvhicl'i-v tends to forma methylol or substi tuted methylol group.

Apparently there is "no similar. limitation in regard to the resins-employed in the aforementioned Bruson Patent 2,031,557, for the reason that one-may; prepare suitable resins from, phenolsof the 'kind already specified which invariablynand inevitably would yield-aresin: having a functionality greater thantwodnitheiultirnate resin :molecule.

The'resins h'ereiniemployed" 'are soluble' in: a. non=oxy- 5. genated hydrocarbon solvent, such as benzene or xylene. As pointed out in the aforementioned Bruson Patent 2,031,557, one of the objectives is to convert the phenolaldehyde resins employed as raw materials in such a way as to render them hydrocarbon soluble, i. e., soluble in benzene. The original resins of U. S. Patent 2,031,557 are selected on the basis of solubility in an oxygenated inert organic solvent, such as alcohol or dioxane. It is immaterial whether the resins here employed are soluble in dioxane or alcohol, but they must be soluble in benzene.

The resins herein employed as raw materials must be comparatively low molal products having on the average 3 to 6 nuclei per resin molecule. The resins employed in the aforementioned U. S. Patent No. 2,031,557, apparently need not meet any such limitations.

The condensation products here obtained, whether in the form of the free base or the salt, do not go over to the insoluble stage on heating. This apparently is not true of the materials described in aforementioned Bruson Patent 2,031,557 and apparently one of the objectives with which the invention is concerned, is to obtain a heatconvertible condensation product. The condensation product obtained according to the present invention is heat stable and, in fact, one of its outstanding qualities is that it can be subjected to oxyalkylation, particularly oxyethylation or oxypropylation, under conventional conditions, i. e., presence of an alkaline catalyst, for example, but in any event at a temperature above 100 C. without becoming an insoluble mass.

Although these condensation products have been prepared primarily with the thought in mind that they are precursors for subsequent reaction, yet as such and withoutfurther reaction, they have definitely valuable properties and uses as hereinafter pointed out.

What has been said previously in regard to heat stability, particularly when employed as a reactant for preparation of derivatives, is still important from the standpoint of manufacture of the condensation products themselves insofar that in the condensation process employed in preparing the compounds described subsequently in detail, there is no objection to the employing of a temperature above the boiling point of water. As a matter of fact, all the examples included subsequently employ temperatures going up to 140 to 150 C. If one were using resins of the kind described in U. S. Patent No. 2,031,557 it appears desirable and perhaps absolutely necessary that the temperature be kept relatively low, for instance, between C. and 100 C., and more specifically at a temperature of 80 to 90 C. There is no such limitation in the condensation procedure herein described for reasons which are obvious in light of what has been said previously.

What is said above deserves further amplification at this point for the reason that it may shorten what is said subsequently in regard to the production of the herein described condensation products. As pointed out in the instant invention the resin selected is xylene or benzene soluble, which differentiates the resins from those employed in the aforementioned Bruson Patent No. 2,031,557. Since formaldehyde generally is employed economically in an aqueous phase to solution, for example) it is necessary to have manufacturing procedure which will allow reactions to take place at the interface of the two immiscible liquids, to wit, the formaldehyde solution and the resin solution, on the assumption that generally the amine will dissolve in one phase or the other. Although reactions of the kind herein described'will begin at least at comparatively low temperatures, for instance, 30 C., 40 C., or 0, yet the reaction does not go to completion except by the use of the higher temperatures. The use of higher temperatures means, of course, that the condensation product obtained at the end of the reaction must not be heat-reactive. Of course, one can add an oxygenated solvent such as alcohol, dioxane, various ethers of glycols, or the like, and

produce a homogeneous phase. If this latter procedure is employed in preparing the herein described condensations it is purely a matter of convenience, but whether it is or not, ultimately the temperature must still pass Within the zone indicated elsewhere, i. e., somewhere above the boiling point of Water unless some obvious equivalent procedure is used.

Any reference, as in the hereto appended claims, to the procedure employed in the process is not intended to limit the method or order in which thereactants are added, commingled or reacted. The procedure has been referred to as a condensation process for obvious reasons. As pointed out elsewhere it is my preference to dissolve the resin in a suitable solvent, add the amine, and then add the formaldehyde as a 37% solution. However, all three reactants can be added in any order. I am inclined to believe that in the presence of a basic catalyst, such as the amine employed, that the formaldehyde produces methylol groups attached to the phenolic nuclei which, in turn, react with the amine. It would be immaterial, of course, if the formaldehyde reacted with the amine so as to introduce a methylol group attached to nitrogen which, in turn, would react with the resin molecule. Also, it would be immaterial if both types of compounds Were formed which reacted with each other with the evolution of a mole of formaldehyde available for further reaction. Furthermore, a reaction could take place in' which three difierent molecules are simultaneously involved although, for theoretical reasons, that is less likely. What is said herein in this respect is simply by way of explanation to avoid any limitation in regard to the appended claims.

Actually, what has been said previously is not as complete an idealized presentation as is desirable due to another factor involved. The factor is this. Since the polyamine is hydroxylated and although it may have a tertiary amine group which is not susceptible to oxyalkylation, it may have more than one secondary group and thus the amine residue per se is certain to have at least one hydroxyl group and perhaps more than one and may have a labile hydrogen atom attached to nitrogen. Actually, it is difiicult to state in general terms What the susceptibility of a secondary nitrogen group is under the conditions described for reasons which are obscure. Briefly stated, oxyalkylation seems to proceed readily at terminal secondary amino groups but less readily and sometimes hardly at all when the same group appears in the center of a large molecule. In the instant situation there are phenolic hydroxyl groups available which are readily susceptible to oxyalkylation and also hydroxyl groups in the amino radical. If one assumes for the moment that the hydroxylated amine radical contains at least one or possibly two hydroxyls and if one ignores the oxyalkylation susceptibility of any secondary amino groups present, then the condensate can be depicted more satisfactorily in the following manner by first referring to the resin condensate and then to the oxyalkylated derivative:

previous significance,

in which for simplicity .the formula just shown previously has been limited to the specific instance where there is one oxyalkylation susceptible hydroxyl radical as part of the polyamine residue.

Inthe above. formula.RO is the radical of an alkylene oxide such as the ethoxy, .propoxy or similar radicals derived from ethyleneoxide, propylene oxide, glycide or the like, and n is a number varying from 1 to 60, with the provisothat one need notoxyalkylate all .the available phenolichydroxyl radicals orall the available amino hydrogen atoms to .theextent they arepresent. In other words, one need convert only two labilehydrogen radicals, per condensate. Itis immaterial whether the labile hydrogen atomsbe attached to oxygen or nitrogen.

Oneimportant use of the herein'described products is in the resolution of petroleum emulsions of the water-in-oil type.

As .far as the use of the herein described products goes for purpose of resolution of petroleum emulsions of the water-in-oil type, I particularly prefer to use those which as such or inthe form of the free base or hydrate, i. e., combination with water or particularly in the form of a low molal organic acid suchv as the acetate or hydroxy acetate, have sufficiently hydrophilecharacter to at least meet the test set forth in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote et al. In said patent such test for emulsificationusing a water-insoluble solvent, generally xylene, is described as an index of surface activity.

.In the present instance the various condensation products as such or in the form of the free. base .or in the form of the acetate, maynotnecessarily be xylene-soluble although they are in many instances. If such compounds are. not xylene-soluble the obvious chemical equivalent or equivalent chemical test. can be made by simply using some suitable solvent, preferably. a water-soluble solvent s'uch as ethylene glycol .diethylether, or a low molal. alcohol, or a mixture to dissolve theappropriate product being examined and then mix with the. equal weight of xylene, followed by addition of water. Such test is obviously the same for the reason that there will be two phases on vigorous shaking and surface. activity makes its: presence manifest. It is understood that reference in the hereto appended claims as .to the use of xylene in. the emulsification test includes such obvious variant.

Reference is again made to U. S. Patent 2,499,368, dated March 7, 1950, to De Groote and Keiser. In said immediately aforementioned patent the following test appears:

The same is true in regard to the oxyalkylated resins herein specified, particularly in the lower stage of oxyalkylation, the so-called subsurface-active stage. The surface-active properties are readily demonstrated by producing a xylene-water emulsion. A. suitable procedure is as follows: The oxyalkylated resin is dissolved in an equal weight of xylene. Such'SO-SO solution is then mixed with 1-3 volumes of water and shaken to produce an emulsion. The amount of xylene is invariably sufficient to reduce even a tacky resinous'product to a solution'" which is readily disper'sible. The emulsions so, produced are usually xylene-in-Water emulsions (oil-in-water type) particularly when the amount of distilled water used is at least slightly in. excess of the volume of xylene solution-and. also if shaken vigorously. At times, particularly. inthe lowest stage :of oxyalkylatiomone mayobtain a water-in-xylene emulsion (water-in-oil type) which is .apt to reverse on more vigorous shaking and 'further dilution with water. Ifin doubtas to this property, comparison with a resin obtained from para-tertiary butylphenol and formaldehyde (ratio 1 part phenol to 1.1 formaldehyde) using an acid catalyst and then followed by oxyalkylation .using 2,moles of ethylene oxide" for each phenolic hydroxyl, is helpful. Such resin prior to oxyalkylation has .a moleculanweight indicating .about 4% units per resin molecule. Such resin, whendilutd with an equal weight of xylene, will serve to illustrate the above emulsification test.

In a few instances, the resin may not be sufficiently soluble in xylene alone but may require the addition'of some ethylene glycol diethylether as described elsewhere. It is understood that such mixture, or any other similar mixture, is considered the equivalent of xylene for'lthe purpose'of this test.

In many cases, there is no doubt as to the presence orabsence of hydrophile or surface-active characteristics in the products .used in accordance with this invention. They dissolve or disperse in water; and such dispersions foam readily. With borderline cases, i. e., those which show only incipient hydrophilev or surface-active property (subsurface-activity) tests'for emulsifying properties or self-dispersibility are useful. The fact that a reagent is capable of producing a dispersion in water is proof that it is distinctly hydrophile. In doubtful cases, comparison can be made with the butylphenol-formaldehyde resin analog wherein 2 moles of ethylene oxide have been introduced for each phenolic nucleus.

The presence of xylene or an equivalent water-insoluble solvent may mask thepoint at which a solvent-free product on mere dilution in a test tube exhibits self-emulsification. For this reason, if it isdesirable to determine the approximate point where self-emulsification begins, then it is better to eliminate thexylene or equivalent from a small portion of the reaction mixture. and test such portion. 'In some cases, such xylene-free resultant may show initial or incipient hydrophile properties, whereas in presence of xylene such properties would not be noted. In other cases, the first objective indication of hydrophileproperties may be the capacity of the material toemulsify an insoluble solvent such as xylene. It is to be emphasized that hydrophile properties herein referred toare such as those exhibited by incipient self-emulsification or the presence of emulsifyingproperties and go through the range of homogeneous dispersibility or admixture with water even in presence of addedwater-insoluble solvent and minor proportions of common electrolytes as occur in oil field brines.

Elsewhere, it is pointed out that an emulsification test may be .used to determine ranges of surface-activityarid that such emulsification tests employ a xylene solution.

Stated. another way, it is really immaterial'whether a. xylene solution produces a sol or whether it merely produces an emulsion.

Havingdescribed the invention briefly and not necessarily in its. most complete aspect,. the text. immediately'following will :be a morecomplete description with specific reference to reagents and the method of manufacture.

For convenience the subsequent text will bedivided into five parts:

Part 1 is concerned with the general structure of .the amine-modified resin condensates and also the resin itself, which is used as a raw material;

- Part 2 is. concerned with appropriate basic hydroxylated polyamines which. may be employed. in. the. preparation 1952, for both purpose of convenience and comparison.

b, PART 1 I It is well known that one can readily purchase on the open market, or prepare, fusible, organic solvent-soluble, water-insoluble resin polymers of a composition approximated in an idealized form by the formula In the above formula n represents a small whole number varying from 1 to 6, 7 or 8, or more, up to probably 10 or 12 units, particularly when the resin is subjected to heating under a vacuum as described in the literature. A limited sub-genus is in the instance of low molecular weight polymers where the total number of phenol nuclei varies from 3 to 6, i. e., n varies from 1 to 4; R represents an aliphatic hydrocarbon substituent, generally an alkyl radical havingfrom 4 to 14 carbon atoms, such as a butyl, amyl, hexyl, decyl or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

Because a resin is organic solvent-soluble does not mean it is necessarily soluble in any organic solvent. This is particularly true where the resins are derived from trifunctional phenols as previously noted. However, even when obtained from a difunctional phenol, for instance para-phenylphenol, one may obtain a resin which is not soluble in a nonoxygenated solvent, such as benzene, or xylene, but requires an oxygenated solvent such as a low molal alcohol, dioxane, or diethylgylcol diethylether. Sometimes a mixture of the two solvents (oxygenated and nonoxygenated) will serve. See Example 9a of U. S. Patent No. 2,499,365, dated March 7, 1950, to De Groote and Keiser.

The resin herein employed as raw materials must be soluble in a nonoxygenated solvent, such as benzene or xylene. This presents no problem insofar that all that is required is to make a solubility available resins, or else prepare resins which are xylene or benzene-soluble as described in aforementioned U. S. Patent No. 2,499,365, or in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Keiser. In said patent there are described oxyalkylation-susceptible, fusible, nonoxygenated-organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resins having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctionalonly in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula Serial No. 288,745, filed May 19,.

test on commercially one of the occurrence of R.

in whic'h R is an aliphatic hydrocarbon radical having at least 4 carbon atoms and not more than 24 carbon atoms, and substituted in the 2,4,6 position.

"If one selected a resin of the kind just described pre viously and reacted approximately one mole of the resin with two moles of formaldehyde and two moles of a basic nonhydroxylated secondary polyamine as specified, following the same idealized over-simplification previously referred to, the resultant product might be illustrated thus:

on 011 OH 12' si N H H R a The basic polyamine may be designated thus:

subject to what has been said previously as to the presence of at least one amine radical in at least one occurrence of R with the proviso, 'as previously stated, that the amine radical be other than a primary amine radical, a substi tuted imidazoline radical or a substituted tetrahydropy-' rimidine radical, with the proviso that there must be present at least one hydroxyl radical as part of at least However, if one attempts to incorporate into the formula a structure such as an oxyethylated or oxypropylated derivative of a substituted polyalkyleneamine of the following type:

a l n N'GnH'Zn.(CnH2nN. D)IN RI! R" in whichthe various characters have the same significance as in initial presentation of this formula, then one becomes involved inadded difliculties in presenting an overall picture. Thus, for sake of simplicity, thehydroxylated polyamine will be depicted as l t HN the resin molecule, or even to a very slight extent, if at all, 2 resin units may combine Without any amine in the reaction product, as indicated in the following formulas:

OH OH 1 10H 1 R141 RIII O R R n R in which R' is the divalent radical obtained from the particular aldehyde employed to form the resin. For reasons which are obvious the condensation product obtained appears to be described best in terms of the method of manufacture.

As previously rstated .the preparation of resins,'::.the.kind herein employed as reactants, is Well known. See previously mentioned U. S. Patent 2,499,368. Resins can be made using an acid catalyst or basic catalyst or a catalyst having neither acid nor basic properties in the ordinary sense or withoutany catalyst at all. Itispreterable that the resins employed be substantially .neutral. Inother words, iii-preparedby using a strong acid-as a catalyst, such: strong acid should be neutralized. Similarly, if a strong: base is used as a catalyst it. is preferablethat the base be neutralizedalthough I have found that sometimes the reaction described proceeded more rapidly in the presence of a small amount of a free'base. Theamount may be as small as a 200th of a percent and. as much as a few 10ths of a percent. Sometimes moderate increase in caustic soda and caustic potash may be used. However, the most desirable procedure in practically every case is to have the resin neutral.

"In preparing resins one does not geta singlepolymer, i.-e., onevhaving just 3 units, or just'4 .units, or just 5 units, or just 6 units, etc. It is usually a mixturegfor instance, one approximating 4 phenolic nuclei will have some trimer and pentamer present. Thus, the molecular weight may be such that it corresponds to a fractional value for n as, for example, 3.5, 4.5 or 5.2.

"In the actualmanufacture of'the resins I foundno reason for using other than those which are lowest in price and most readily available commercially. For purposes of convenience suitable resins are characterized in the following table:

TABLE I 4 M01. wt Ex Position 11' derived R n of resin N 0. at R from moleule 1a,, Nonyl; Para. Formaldehydel 4. 8 1, 570. 4 Tertiarybutylun d do 3. 882. 5 Secondary butyl. 6.5 882. 5 CyClOheXyL... .l 3. 5 1,025. 5 Tertiary amyL... 3. 5 959. 5 Mixed secondary 3. 5 805. 5

and tertiary .amy Propyl. 3. 5 S05. 5 Tertiary hex 3. 5 1,?036. 5' Octyl. 3.5 1,190. 5 Nonyl. 3.5 1,267.5 Deeyl.. 3. 5 1, 34.4. 5 Dodecyl .l 3. 5 1, 498. 5 Tertiary butyl. 3. 5 945. 5 Tertiary amyl 3. 5 1, 022. 5 Non 1 3. 5 1,330. 5 Tertiary butyl. 3. 5 1, 071. 5 Tertiary amy 3. 5 1, 148. 5 Nonyl 3. 5 1, 456. 5 Tertiary hutyl, 3. 5 1,008.5 Tertiary amyL. 3. 5 1, 085.5 011 l 3. 5 l, 393. 5 Tertiary buty '4. 2 996. 6 Tertiary amyl 4. 2 1,083. 4 Nouyl 4. 2 1, 430. 6 m; Tertiary butyl. 4. 8 1, 094. 4 26a... Tertiary amyl 4.8 1,189.6

PARTI 2 Ashas been pointed out, the amine herein" employed; as

a. reactant .is ahydroxylated .basic polyamine and-preferably a strongly basic polyamine having at least oneseer ondary amino. radical, free from primary amino ;,groups, freeffrom substitutedirnidazoline groups,.and free. from substituted tetrahydropyrimidine. groups, in which. the .hy,'

drocarbon radicals present, whether monovalent or =divalent are alkyl, .alicyclic, arylalkyl, or heterocyclic in character,. subject of course to the inclusion of a-hydroxyl group attached to a carbon atom Which in turn. is .part of a monovalent or divalent radical.

Previous reference has been made to a numberof polyamines which are satisfactory for use as reactants in theIinstant condensation procedure. They. can be. obtained by hydroxyalkylationof low cost polyamines. 'The 1 cheapest amines available are polyethylene amines and polyp-ropylene'amines. In the case of the polyethylene amines there may be as manyas 5, Ger 7 nitrogenatoms. Such amines are susceptible to terminal 'alkylation or the equivalent, i. e., reactions which convert the terminal primary amino group or groups into a secondary or tertiary amine radical. .In the case of polyamines having at least 3 nitrogen atomsor more, both terminal groups could be converted into tertiary groups, or one terminal group could be converted into a tertiary group and the other into a secondary amine group. In the same way, the polyamincs can be subjected to hydroxyalkylationby reaction with .ethylene oxide, propylene oxide,, glycide, etc. In some instances, depending on the structure,'both types of reaction may be employed, vi. e., one type to-.in troduce a hydroxyl ethyl group, for example, and. another type. to =introduce.a.methyl or ethyl radical.

I By way of example the following formulasareincluded. It will be noted .they include such polyamines which, insteadof being obtained from ethylene dichloride, propyl' cnedichl0ride,..or the, like, are obtained from diohloroethyl others .in which the divalent radical hasacarbon atom .chaiminterrupted by an oxygen atom:

-(H O CzHOz (hHqlfi CzHt (CHL 2 CiHs I, NORHQNCZHAN H'O'C'zHr C 2 1 0 H CH3 CH3 Nozrno ozrnN nocini canon NC7H4O CQIEHN E 0 C 2H4 @1114 0H CH3 CH;

CrHs

. CJHGOH said previously may be illustrated by 13 reactions involving a secondary alkylamine, or a secondary aralkyl amine, or a secondary alicyclic amine, such as dibutylamine, dibenzylamine, i licyclohexylamine, or mixed amines with an imine so as tointroduce a primaryamino group which can be reacted with an 'alkylene oxide-tol lowed by'reaction with an imine and then the use of an alkylene oxide again. Similarly, one can startwith a primary amine and introduce two moles of analkylene oxide so as to have a compound comparable to ethyl diethanolamineand react with two moles of an imine and then with two moles of ethylene oxide.

Reactions involving the same reactants previously described, i."e., a suitable secondary monoamineplus an alkylen'eimine plus an alkylene oxide, ora suitable monoamine plus an alkylene oxide plus an alkylene'imine and plus the'second introduction of an alkylene oxide, can be applied to a variety of primary amines. In the case of primary amines one can either employ two moles of an alkylene oxide so as toconvert both aminohydrogen atoms=intoan alkanol group, or the equivalentj or else the primary amine can be; converted into a secondary amine by-the alkylation-reaction. many event, one can obtain" a "series I of primary amines "and corresponding secondary amines which are characterized by the fact that such amines include groupsfhaving repetitiousether linkages and .thus introduce a definite hydrophile effecthby virtue of-the ether linkage. Suitablejpolyether amines susceptible to conversion in the manner describedinclude those of the formula V[RI(O n h)z] i p p NH intwhichm is asmall whole number having a value of 1 ormore, andmay be as much as. 1001 12; n. is an integer having a valued 21to;4, inclusive; m representsthe numeral 1 to 2; and m represents a number to l, with the proviso that thesum ofm plus m equals 2; and R has its prior significance, particularly as a hydrocarbon radical. The preparation ;of;such amines has been described 'in' the literature and particularly. in two United States patents, to-wit U. S. Nos. 2,325,514, dated July 27, '1943, to Hester,..and 2,355,337, dated August 8, .1944 to Spence. The latter patent describes typical haloalkyl ethers such as T ontooamol CHa-CH2 H it CQH,OC H4OC,H4OCHH 4OCQHiCl' Such-haloalkyl ethers can react with ammonia, or with a primary amine such as methylamine, ethylamine, cyclohexylamine, etc., to produce a secondary amine of the kind above described, in which'one of the groups attached to nitrogen is typified by. R. ethers also canbe reacted with ammonia to give second ary amines as described in the first of the two patents mentioned immediately preceding. Monoamines so obtained' and suitable forconversion into appropriate polyamines are exemplified by (CI-IaOCHzCI-IzCHzCHzCHzCHzhNI-I ther similar secondary monoamines equally suitable for such conversion reactions inorder to yield appropriatesecondar'y amines, are thos e ofthe composition rt-0mm);

li -owner as described in U. s. Patent No. 2,375,659, dated May 8, 1945, to Jones et al. In the above formula R be methyl, ethyl, propyl, amyl, octyl,"etc. "Other suitable secondary amineswhich can be con- Such haloalkyl verted into appropriate polyamines can be obtained from products which are sold in the open market, such as may be obtained by alkylation of cyclohexylmethylarnine or the alkylation of similar primary amines, or for that matter, amines of the kind described in U. S. Patent No. 2,482,546 dated September 20, 1949, to Kaszuba, provided there is no negative group or halogen attached to the phenolic nucleus. Examples include the following: beta phenoxyethylamine, gamma phenoxypropylamine, beta-phenoxy-alpha-methylethylamine, and beta-phenoxypropylamine.

Other secondary monoamines suitable for conversion into polyamines are the kind describedin British Pat ent No. 456,517, and may be illustrated by In light of the various examples of polyamines which have been used for illustration it may be well to refer again to the fact that previously-the amine was shown as with the statement that. such presentation is an oversimplification. It was pointed out that at least one 0c- H C H: /N--propyleneNpropylene N In the first of the two above formulas if the reaction involves a terminal amino hydrogen obviously the radicals attached to the nitrogen atom, which in turn combines with the methylene bridge, would be different than if the reaction took place at the intermediate secondary amino radical as diiferentiated from the terminal group. Again, referring to the second formula above, although a terminal amino radical is not involved it is obvious again that one could obtain two different structures for the radicals attached to the nitrogen atom unitedto the methylene bridge, depending on whether the reaction took place at either one of the two outer secondary amino groups, or at the central secondary amino group If there are two points of reactivity towards formaldehyde as illustrated by the above examples it is obvious thatone might get a mixture in which in part the reaction took place at one point and in part at another point. Indeed, there are well known suitableipolyamine reactions where a large variety of compounds might be obtained due to such multiplicity of reactive radicals. This can be illustrated by the following formula CH; i

\NC ZHJN flHiNO zHaNC eHiN H H ozHtoH Certain hydroxylated polyamines which may be employed and which illustrate the appropriate type of reactant used for the instant condensation reaction may be illustrated-by the following additional examples:

N-C morn-sr-crnom-on n n noontoHmm-omcrrr-Nncmonlon area-ass;

j -Asis welliknown' one can prepare'ether amine alcohols of ..-the. type The-t products obtained by flthe: herein I describedaproc esses represent cogeneric mixtures which. are the result of a condensation reaction or reactions. "Since the resin molecule cannot *be* defined -satisfactorily by formula, although it may be so illustrated in an idealized simplifi' cation, it is difficult to actually depict the final product I solvents are not here included as raw materials.

16 of..the cogeneric mixture except in terms of-the; process itself. 1

Previous. reierencehas beenwmade to..the .fact. that. the procedure. herein employed. is comparable, in aa: general way, to -/that whichcorresponds to somewhatsimilar derivatives .made either from phenols as differentiated fromarresin, orl-in. the manufacture of a phenol-amine aldehyde resin; orelse from a particularly selected resin andan amineand formaldehyde in the manner described in Brunson Patent No. 2,031,557 in order to obtainaheatreactive resin. Since the condensation products obtained are notUheat-conver-tible and sincemanufacture is-i not restrictedtoasingle .phase system, and since temperaturesup to. C. or'thereabouts may be employed, sis-sis obvious that rzthe procedure becomes comparatively, simple. Indeed, perhaps"no description is necessary over and above what 'has been. said previously,.zin.-,light. of. subsequent examples. However, forpurposesofsclarity thefollowing.detailsxarejncluded.

- A convenient piece of equipment .for preparationnof: these..cogeneric..mixturesis .a resin- .pot of the..kind de-,= scribed .in aforementioned U.. .S. Patent No. 2,499,368. In..m0st instancesthe. resin selected isnot-apt 'tOubGra' fusible .liquidat thesearlyor low. temperature stage :ofitreactionif. employedlas subsequently describedpinkfaqtr usually) it isaptto be. a solid atvdistinctly.highen tern; peratures, for ..instance,, ordinary room temperature. Thus, I :have. found. it convenient.to.;use-a .solventaand particularly one which can be removed. readilytataa corm paratively moderate temperature, for instance, at 150 C. A suitable solvent is usually-benzene, xylene, or a comparable petroleum'hy'drocarbon 01 a mixture of such or similar solvents. 'Indeed, resins which are not soluble except in oxygenated solvents or mixtures containing such The reaction: can be conducted insuch a'way'that the'initialireaction; and perhaps 'the' bulk of the reaction; takes place inaipolypha'se' system. However, if desirable, one-can use an --oxygenated solvent such-as a low boiling'alcohol, including eth'ybalc'oh'ol, methyl alcohol, etc. "Higher alcoholscanbe used or one can use a comparatively-nonvolatile-solventsuchas dioxane or 'the diethyletherof ethylene glycol. One'can also use a mixture ofbenzene' or xylene and such'oxygenatedsolvents. Note 'that'the use of such oxygenated solvent is not required in the sense that it is not necessary to use an' initial resin "which is soluble only in any oxygenated solvent as just noted, and it is not necessary to have a single phase. system for reaction.

Actually, water'is aptto be present/as a solvent for the reason that in most cases aqueous formaldehyde is employed, whichrmay be the. commercial product which is approximately 37%, or it may bediluted .dovvnHto about 30%.I formaldehyde. However, paraformaldehyde can be used but it ismore difficultperhaps to add aisolid material .instead of the liquid solution and,.everything else being equal, the latter is.apt to be more economical. In any event, water is,prescnt-.as water of reaction. ,lf the solvent is completely removed at the endof the process, no, problem is. involved if the material is-..us'ed for any subsequent reaction. "Howevenif therea'etion mass is going'to be subjected tosQme'Ifurther reaction where the solvent may be objectionable, asin the case or ethyl or hexylualcohoh and ifthere isto besubsequent oxyalkylatiom. then, obviously, the alcohol shouldnot. be usedorelseiit should. be removed. .The fact .that an oxygenatedsolvent. .need not. be employed, of .course, is an advantage for reasons stated.

Another factor, as faras the selection of. solvent goes, is whether or not theieogeneric mixture obtained at the end of the reaction is to be-.used as such or in the salt form. The cogeneric mixtures obtained are apt to be solidsior fthick" viscous liquids in which .there'issom'e: change from the. initial. resin .itself,,.particularly. it. some of the, initial solvent .is .apt to. remain without. complete removal. Even if the one starts with a resin which is almost water-white in color, the products obtained are almost invariably a dark red in color or at least a redamber, or some color which includes both an amber component and a reddish component. By and large, the melting point is apt to be lower and the products may be more sticky and more tacky than the original resin itself. Depending on the resin selected and on the amine selected the condensation product or reaction mass on a solventfree basis may be hard, resinous and comparable to the resin itself.

The products obtained, depending on the reactants selected, may be water-insoluble or water-dispersible, or water-soluble, or close to being water-soluble. Water solubility is enhanced, of course, by making a solution in the acidified vehicle such as a dilute solution, for instance, a 5% solution of hydrochloric acid, acetic acid, hydroxyacetic acid, etc. One also may convert the finished product into salts by simply adding a stoichiometric amount of any selected acid and removing any Water present by refluxing with benzene or the like. In fact, the selection of the solvent employed may depend in part whether or not the product at the completion of the reaction is to be converted into a salt form.

In the next succeeding paragraph it is pointed out that frequently it is convenient to eliminate all solvent, using a temperature of not over 150 C. and employing vacuum, if required. This applies, of course, only to those circumstances where it is desirable or necessary to remove the solvent. Petroleum solvents, aromatic solvents, etc., can be used. The selection of solvent, such as benzene, xylene, or the like, depends primarily on cost, i. e., the use of the most economical solvent and also on three other factors, two of which have been previously mentioned; (a) is the solvent to remain in the reaction mass without removal; ([1) is the reaction mass to be subjected to further reaction in which the solvent, for instance, an alcohol, either low boiling or high boiling, might interfere as in the case of oxyalkylation; and the third factor is this, is an effort to be made to purify the reaction mass by the usual procedure as, for example, a water-wash to remove the water-soluble unreacted formaldehyde, if any, or a water-wash to remove any unreacted Water-soluble polyamine, if employed and present after reaction. Such procedures are well known and, needless to say, certain solvents are more suitable than others. Everything else being equal, 1 have found xylene the most satisfactory solvent.

1 have found no particular advantage in using a low temperature in the early stage of the reaction because, and for reasons explained, this is not necessary although it does apply in some other procedures that, in a general way, bear some similarity to the present procedure. There is no objection, of course, to giving the reaction an opportunity to proceed as far as it will at some low temperature, for instance, 30 to 40 but ultimately one must employ the higher temperature in order to obtain products of the kind herein described. If a lower temperature reaction is used initially the period is not critical, in fact, it may be anything from a few hours up to 24 hours. I have not found any case Where it was necessary or even desirable to hold the low temperature stage for more than 24 hours. In fact,- I am not convinced there is any advantage in holding it at this stage for more than 3 or 4 hours at the most. This, again, is a matter of convenience largely for one reason. In heating and stirring the reaction mass there is a tendency for formaldehyde to be lost. Thus, if the reaction can be conducted at a lower temperature so as to use up part of the formaldehyde at such lower emperature, then the amount of unreacted formaldehyde is decreased subsequently and makes it easier to prevent any loss. Here, again, this lower temperature is not necessary by virtue of heat convertibility as previously referred to.

If solvents and reactants are selected so the reactants and products of reaction are mutually soluble, then agitation is required only to the extent that it helps cooling or helps distribution of the incoming formaldehyde. This mutual solubility is not necessary as previously pointed out but may be convenient under certain circumstances. On the other hand, if the products are not mutually soluble then agitation should be more vigorous for the reason that reaction probably takes place principally at the interfaces and the more vigorous the agitation the more interfacial area. The general procedure employed is invariably the same when adding the resin and the selected solvent, such as benzene or xylene. Refiuxing should be long enough to insure that the resin added, preferably in a powdered form, is completely soluble. However, if the resin is prepared as such it may be added in solution form, just as preparation is described in aforementioned U. 3. Patent 2,499,368. After the resin is in complete solution the polyamine is added and stirred. Depending on the polyamine selected, it may or may not be soluble in the resin solution. If it is not soluble in the resin solution it may be soluble in the aqueous formaldehyde solution. If so, the resin then will dissolve in the formaldeiyde solution is added, and if not, it is even possible that the initial reaction mass could be a three-phase system instead of a two-phase system although this would be extremely unusual. This solution, or mechanical mixture, if not completely soluble is cooled to at least the reaction temperature or somewhat below, for example 35 C. or slightly lower, provided this initial low temperature stage is employed. The formaldehyde is then added in a suitable form. For reasons pointed out I prefer to use a solution and whether to use a commercial 37% concentration is simply a matter of choice. In large scale manufacturing there may be some advantage in using a 30% solution of formaldehyde but apparently this is not true on a small laboratory scale or pilot plant scale. 30% formaldehyde may tend to decrease any formaldehyde loss or make it easier to control unreacted formaldehyde loss.

On a large scale if there is any difiiculty with formaldehyde loss control, one can use a more dilute form of formaldehyde, for instance, a 30% solution. The reaction can be conducted in an autoclave and no attempt made to remove water until the reaction is over. Generally speaking, such a procedure is much less satisfactory for a number of reasons. For example, the reaction does not seem to go to completion, foaming takes place, and other mechanical or chemical difficulties are involved. I have found no advantage in using solid formaldehyde because even here water of reaction is formed.

Returning again to the preferred method of reaction and particularly from the standpoint of laboratory procedure employing a glass resin pot, when the reaction has proceeded as one can reasonably expect at a low temperature, for instance, after holding the reaction mass with or without stirring, depending on whether or not it is homogeneous, at 30 or 40 C. for 4 or 5 hours, or at the most, up to 10-24 hours, I then complete the reaction by raising the temperature up to 150 C., or thereabouts as required. The initial low temperature procedure can be eliminated or reduced to merely the shortest period of time which avoids loss of polyamine or formaldehyde. At a higher temperature I use a phase-separating trap and subject the mixture to reflux condensation until the Water of reaction and the water of solution of the formaldehyde is eliminated. I then permit the temperature to rise to somewhere about C., and generally slightly above 100 C., and below C. by eliminating the solvent or part of the solvent so the reaction mass stays Within this predetermined range. This period of heating and refluxing, after the Water is eliminated, is continued until the reaction mass is homogeneous and then for one to three hours longer. The removal of the solvents is conducted in a conventional manner in the same Way as the removal of solvents in resin manufacture as described in aforementioned U. S. Patent No. 2,499,368.

product assuch, i. e.,'the anhydro base.

assess Needless to say, as far as the ratio of reactants goes have invariably employed approximately one mole of the resin based on the molecular weight of the resin molecule, 2 moles of the secondary polyamine and 2 moles of formaldehyde. In some instances 1 have added trace of caustic as an added catalyst but have found no particular advantage in this. in other cases I have used a slight excess of formaldehyde and, again, have not found any particular advantage in this. In other cases, I liave used a sli ht excess of amine and, again, have not found anyparticular advantage in so doing. Whenever feasiblel have checked the completeness of reaction in the usual ways, including the amount of water of reaction, molecular weight, and particularly in some instances have checked whether or not theend-product showed surfaceactivity, particularly in a dilute acetic acid solution. The nitrogen content after removal of unreacted polyamine, if ;any is present, is another index.

in the hereto attached claims reference is made to the Needless to sa the hydrated base, i. e., the material as it combines with water or the salt form, with a combination of suitable acids as noted, is essentially the same material but is merely another form and, thus, the claims are intended to cover all three forms, i. e., the'anhydro base, the free base, and the salts.

In light of what has been said previously, little more need be said as to the actual procedure employed for the preparation of the herein described condensation products. The following example will serve by way of illustration:

Example 1 b .resin was perpared using an acid catalyst which was completcly neutralized at the end of the reaction. The molecularweight of the resin was 882.5. This corresponded to an average of about 3 /2 phenolic nuclei, as the value for 'n which excludes the 2 external nuclei, i. e., the resin was largely a mixture having 3 nuclei and 4 nuclei excluding the 2 external nuclei, or 5 and 6 overall nuclei.

. was a 30% solution and the amount employed was 200 grams. it was added in a little over 3 hours, The i'nixture was stirred vigorously and 'kept 'within a temperature range of 33 to 48 C. for about 17 hours. At the end of this time it was refluxed using a phase-separating trap and a small amount of aqueous distillate withdrawn from time to time. The presence of formaldehyde was noted. Any unreacted formaldehyde seemed to disappear within about 3 hours or thereabouts. As soon as the odor of formaldehyde was no longer particularly noticeable or detectible the phase-separating trap was set so as to eliminate part of the xylene until the temperature reached approximately 150 C. or perhaps a little higher. The reaction mass was kept at this temperature for a little over hours and the reaction stopped. During this time any additional water, which was probably water of reaction which had formed, was eliminated by means of the trap. The residual xylene 'was permitted to stay in the cogeneric mixture. A small amount of the sample was heated on a water bath to remove the excess xylene. The residual material was dark red in color and had the consistency of a sticky fluid or tacky resin. The overall time for reaction was somewhat under 30 hours. In other examples it varied from 24 to more than 36 hours. The time can be reduced by cutting the low temperature period to approximately 3 to 6 hours. Note that in Table II followingther'e are a large number of added examples illustrating the same procedure. In each case the initial mixture was stirred 'andh'eld at a fairly low temperature (30 to 40 C.) for a period of several'hours. Then refluxing was employed until the odor of formaldehyde disappeared. After the odor of formaldehyde disappeared the phase-separating trap was employed to separate out all the water, both the solutionand condensation. After all thewater had been separated'enough xylene was taken out to have the final product reflux for several hours somewhere in the range of 145 to 150 'C., or thereaboutsv Usually the mixture yielded acl'e'ar solution by the time the bulk of the water, or 'all of the water, had been removed.

Note that as pointed out previously, this procedure is illustrated by 24 examples in Table II.

TABLE I1 Strengthoi Reaction Max. 0 is- Resin Amt.. h Solvent. used ,Bcaetlcn time tn temp Ex. No. used gm Amine used and amount Sfgfimggl; ayge and amt v temp" (hm) D 0 2a 882 Amine A, 296 g 30%, 200 Xylene, 500 g 21-24 24. 1 0 6a 480 Amine A, 148 g Xylene, 480 g.. 20-23 27 106 633 Amine A, 8 g. Xylene, 610 g 22-27 25 2a 441 Amine B, 176 g... Xylene, 300.g 20-25 s his 5a 480 Amine B, 176 g Xylene, 425 g 23-27 54 10c G33 Amine B, 176 Xylene, 500 g 25-27 30 132 2a 882 .A mine 0, 324 g. Xylene, 625 g 23-26 38 141 5a 480 Amine C, 162 g Xylene, 315 {1 20-21 2-5 10:1 633 Amino C, 162 g... Xylene, 535 g 23-24 1 0 1311 473 Amine D, 256 g Xylene, 425 g 22-25 2 148 14a 511 Amino I), 256 g. Xylene, 450 g 20-21 2a 5 15a 065 Amine D, 256 g. 21-25 28 11.! 2a 441 Amine E, 208 g 22-24 56 143 5a 480 Amine E, 208 g 25-27 06 144 9a '595 Amine E, 208 g..- 26-21 34 141 2a 441 Amine F, 236 21-23 25 153 6a 480 Amine F, 236 g 20-22 28 14a 511 Amine F, 230 g 23-25 27 135 22a 409 Amine G, 172 g 20-21 150 2311 542 Amine G. 172 20-24 as 1:32 25a 547 Amine H, 221 g 20-22 0. 1:? 2a 441 Amine H, 221 g. 20-28 24 14, 2611 595 Amine I, 172 g.... 20-22 32 151 in 391 Amine I, 86 g 30%, 50 Xylene, 300 g 20-20 36 l 11 The resin so obtained in a neutral state had a light amber color.

882 grams of the resin identified as 2a perceding, were powdered and mixed with a considerably lesser weight 0 Amine A- As to the formulas of the above amines referred to as Amine A through Amine I, inclusive, see immediately following:

, hermit .B HOCsHo CsHnOH Amine B- N 0 9H4N 1 Amine o no 02H; 2 canton Norton 3 n Amine D- CH2-CH2 CHr-CH; H-0H no-Nn-cmom-Nn-on Ho-0rr oH, e era-oh.

CH3 H N(C2H40H)2 Amine E- H-( 3-N-CHrC-CH CH1: CH2

Amine F- Amine G HOCHrOHzNH-CHrCHOHCH2-NHCH2CH2OH Amine H- HO CH2OHQNH-CH2 HO CHzCHrNH- H HOCH2CH7NH-CH2 Amine I CHaNHCH:

CHllNHOHT-COHROH CHsNHCHa PART 4 In preparing oxyalkylated derivatives of products of the kind which appear as examples in Part 3, I have found it particularly advantageous to use laboratory equipment which permits continuous oxypropylation and oxyethylation. More specific reference will be made to treatment with glycide subsequently in the text. The oxyethylation step is, of course, the same as the oxypropylation step insofar that two low boiling liquids are handled in each instance. What immediately follows refers to oxyethylation and it is understood that oxypropylation can be handled conveniently in exactly the same manner.

The oxyethylation procedure employed in the preparation of derivatives of the preceding intermediates has been uniformly the same, particularly in light of the fact that a continuous operating procedure was employed. In this particular procedure the autoclave was a conventional jacketed autoclave, made of stainless steel and having a capacity of approximately 25 gallons, and a working pressure of 300 pounds gauge pressure. The autoclave was equipped with the conventional devices and openings, such as the variable speed stirrer operating at speeds from 50 R. P. M. to 500 R. P. M., thermometer well and thermocouple for recorder controller; emptying outlet, pressure gauge, manualand rupture disc vent lines; charge hole for initial reactants; at least one connection for conducting the incoming alkylene oxide, such as ethylene oxide, to the bottom of the autoclave; along with suitable devices for both cooling and heating the autoclave through the jacket. Also, I prefer coils in addition thereto, with the coils so arranged that they are suitable for heating with steam or cooling with water, and the jacket further equipped With electrical heating devices, such as are employed for hot oil or Dowtherm systems. Dowtherm, more specifically Dowtherm A, is a colorless non-corrosive liquid consisting of an eutectic mixture of diphenyl and diphenyl oxide. Such autoclaves are, of course, in essence, small scale replicas of the usual conventional autoclave used in commercial oxyalkylating procedure.

Continuous operation, or substantially continuous operation, is achieved by the use of a separate container to hold the alkylene oxide being employed, particularly ethylene oxide. The container consists essentially of a laboratory bomb having a capacity of about 10 to 15 gallons or somewhat in-excess thereof. This bomb was equipped, also, with an inlet for charging, and an outlet tube going to the bottom of the container so as to permit discharging of alkylene oxide in the liquid phase to the autoclave. Other conventional equipment consists, of course, of the rupture disc, pressure gauge, sight feed glass, thermometer, connection for nitrogen for pressuring bomb, etc. The bomb was placed on a scale during use and the connections between the bomb and the autoclave were flexible stainless hose or tubing so that continuous weighings could be made without breaking or making any connections. This also applied to the nitrogen line, which was used to pressure the bomb reservoir. To the extent that it was required, any other usual conventional procedure or addition which provided greater safety was used, of course, such as safety glass, protective screens, etc.

With this particular arrangement practically all oxyethylations became uniform in that the reaction temperature could be held within a few degrees of any selected point in this particular range. In the early stages Where the concentration of catalyst is high the temperature was generally set for around C. or thereabouts. Subsequently the temperature may besomewhat higher for instance, C. to C. Under other conditions, definitely higher temperatures may be employed, for instance 170 C. to 175 C. It will be noted by examination of subsequent examples that this temperature range was satisfactory. In any case, where the reaction goes more slowly a higher temperature may be used, for instance, 140 C. to C., and if need be C. to C. Incidentally, oxypropylation takes place more slowly than oxyethylation as a rule and for this reason I have used a temperature of approximately 135 C. to 140 C., as being particularly desirable for initial oxypropylation, and have stayed within the range of 130 C. to 135 C. almost invariably during oxypropylation. The lesser reactivity of propylene oxide compared with ethylene oxide can be olfset by use of more catalyst, more vigorous agitation and perhaps a longer time period. The ethylene oxide was forced in by means of nitrogen pressure as rapidly as it was absorbed as indicated by the pressure gauge on the autoclave. In case the reaction slowed up the temperature was raised so as to speed up the reaction somewhat by use of extreme heat. If need be, cooling water was employed to control the temperature.

As previously pointed out in the case of oxypropylation as differentiated from oxyethylation, there was a tendency for the reaction to slow up as the temperature dropped much below the selected point of reaction, for instance, 135 C. In this instance, the technique employed was the same as before, that is, either cooling water was cut down or steam was employed, or the addition of propylene oxide speeded up, or electric heat used in addition to the steam in order that the reaction proceeded at, or near, the selected temperatures to be maintained.

Inversely, if the reaction proceeded too fast regardless of the particular alkylene oxide, the amount of reactant beingadded, such as ethylene oxide, was cut down or electrical heat was cut off, or steam was reduced, or if need be, cooling water was run through both the jacket and the cooling coil. All these operations, of course, are depending on the required number of conventional gauges, check valves, etc., and the entire equipment,as has been pointed out, is conventional and, as far as I am aware can be furnished by at least two firms who specialize in the manufacture of this kind of equipment.

Attention is directed to the fact that the use of glycide requires extreme caution. This is particularly true on any scale other than small laboratory or semi-pilot plant operations. Purely from the standpoint of safety in the handling of glycide, attention is directed to the following: (a) If prepared from glycerol monochlorohydrin, this product should be comparatively pure; (b) the glycide itse'lfshould be its pure ats possible as the 'etfect of impurities -is diflicult to evaluate; the glycide should be int'r'oduced carefully and precaution should be taken that it reacts as promptly as introduced, i. e., that no excess of' glycide is allowed to accumulate; (d) all necessary precautions should be taken that vglycide cannot polymerize per se; (2) due to 'the high boiling pointof glycide one can readilyemploy a typical separatable glass resin pot as described in U. S. Patent No. 2,499,370, dated March 7, 1950, and offered for sale by numerous laboratory supply houses. If such arrangement is used to prepare laboratory scale duplications, then care should be taken that the heating mantle can be removed-rapidly so as to allow for cooling; or better still, through an added opening at the top, the glass resin pot or comparable vessel should be equipped with a stainless steel cooling coil so that the pot can be cooled more rapidly than mere removal of mantle. If a stainless steel coil is introduced it means that conventional stirrer of the paddle type is changed into the centrifugal type which causes the fluids orreactants to mix due to swirling action in the center of the pot. Still better, is the use of a laboratory autoclave of the kind previously described in this part of the text, but in any event, when the initial. amount of glycide is added to a suitable reactant, such as the herein described amine-modified phenol-aldehyde resin, the speed of reaction should'be controlled by the usual factors, such as (a) the addition of glycide; (b) the elimination of'external heat, and (c) use ofcooling coil so there is no undue rise in temperature. All the foregoing is merely conventional but is included due to the hazard in handling 'glycide.

Although ethylene oxide andpropylene oxide may represent less of a hazard thanglycide, 'yet these reactants should be handled with extreme care. One suitable procedure involves the use of propylene oxide or butylene oxide as a solvent as'well as a reactant in the earlier stages along with ethylene oxide, for instance, by dissolving the appropriate resin condensate in propylene oxide even though oxyalkylation is taking place to a greater or lesser degree. After a solution has been obtained which represents the selected resin condensate dissolved in propylene oxide or butylene oxide, or a mixture which includes the oxyalkylated product, ethylene oxide is added to react with the liquid mass until hydrophile properties are obtained, if not previously present to the desired degree. Indeed hydrophilc character can be reduced or balanced by use of some other oxides such asipropylene oxide or butylene oxide. Since ethylene oxide ismore reactive than propylene oxide or butylene oxide, the final product may contain some unr'eacted propylene oxide or butylene oxide which can be eliminated by volatilization or distillation in any suit able manner. See article entitled Ethylene oxide hazards and methods of handling, Industrial and Engineering Chemistry, volume 42, N0. 6, June 1950, .pp. 1251-1258. Other procedures can be employed as, for example, thatdescribed in U. S. Patent No. 2,586,767, dated February-19, 1952, to Wilson.

Example of solvent (xylene) along with onepound of finely pow- "dere'd caustic soda as acatalyst. Adjustment was made 7 in the autoclave to 'op'e r'ate at a temperature'of approximately 130 C. to 135 C.,*and at a pressure of about resin condensate was 54.7 to 1.

24 15 to 20 pounds. In some subsequent examples pressures up to 35 pounds were employed.

The time regulator was set so as to inject the ethylene oxide in approximately 1% hours, and then continue stirring for 15 minutes longer. The reaction went readily and, as a matter of fact, the oxide was taken up almost immediately. Indeed the reaction was complete in less than an hour. The speed of reaction, particularly at the low pressure, undoubtedly was due in a large measure to excellent agitation and also to the comparatively high concentration of catalyst. The amount of ethylene oxide introduced was equal in weight to the initial condensation product, to wit, 12.02 pounds. This represented a molal ratio of 27.3 moles of ethylene oxide per mole of condensate.

The theoretical molecular weight at the end of the reaction period was 2404. A comparatively small sample, less than 50 grams, was withdrawn merely for examination as far as solubility or emulsifying power was concerned and also for the purpose of making some tests on various oil field emulsions. The amount withdrawn was so small that no cognizance of this fact is included in the data, or subsequent data, or in the data presented in tabular form in subsequent Tables III and TV.

The size of the autoclave employed was 25 gallons. In innumerable comparable oxyalkylations I have withdrawn a substantial portion at the end of each step and continued oxyalkylation on a partial residual sample. This was not theca'se'in'this particular series. Certain examples were duplicated as hereinafter noted and subjected to oxyalkylation with a diflerent oxide.

Example 20 tion of Example lc,ipreceding. As previously stated, the

'oxyalkyladon-susceptible compound, to wit, Example 112,

present at the beginning of the stage was obviously the same as at the end of the prior stage (Example 10),

about 12.02 pounds. The amount of oxide present in the initial step'was 12.02 pounds, the amount of catalyst remained the same, to wit, one pound, and the amount of solvent remained the same. The amount of oxide added 'was another 12.02 pounds, all addition of oxide in these various stages being based on the addition of this particular amount. Thus, at the end of the oxyethylation step the amount of oxide added was a total of 24.04 pounds and the molal ratio of ethylene oxide to The theoretical molecular weight was 3606.

The maximum temperature during the operation was 'C. to C. I The maximum pressure was in the range of 15 to 20 pounds. The time period was a little less than before, to wit, only 45 minutes.

Example 3c Example 40 The oxyethylation was continued and the amount of oxide added again was 12.02 pounds. There was no added catalyst and no added solvent. The molal ratio of oxide to condensate'was 109 to 1. Conditions as far as temperature and pressure were "concerned were the'same'as in'previousexamples. The time period was 25 slightly longer, to wit, 2% hours. The theoretical molecular weight at the end of the prior step was 4808, and at the end of this step 6010. The reaction showed some slowing up at this particular stage.

Example 50 Example 60 The same procedure was followed as in the previous examples. The amount of oxide added was another 12.02 pounds, bringing the total oxide introduced to 72.12 pounds. The temperature and pressure during this period were the same as before. There was no added solvent. The time period for 3 hours.

Example 70 The same procedure was followed as in the previous six examples without the addition of more caustic or more solvent. The total amount of oxide introduced at the end of the period was 84.14 pounds. The theoretical molecular weight at the end of the oxyalkylation period was 9616. The time required for the oxyethylation was the same as in the previous step, to wit, 3 hours.

Example 80 This was the final oxyethylation in this particular series. There was no added solvent and no added catalyst. The total amount of oxide added at the end of this step was 96.16 pounds. The theoretical molecular weight was 10,818. The molal ratio of oxide to resin condensate was 218 to one. Conditions as far as temperature and pressure were concerned were the same as in the previous examples and the time required for oxyethylation was slightly longer than in the previous step, to wit, 4 hours.

The same procedure as described in the previous examples was employed in connection with a number of the other condensates described previously. All these data have been presented in tabular form in a series of four tables, Tables III and IV, V and VI.

In subsequently every case a 25-gallon autoclave was employed, although in some instances the initial oxyethylation was started in a 15-gallon autoclave and then transferred to a 25-gallon autoclave. This is immaterial but happened to be a matter of convenience only. The solvent used in all cases was xylene. The catalyst used was finely powdered caustic soda.

Referring now to Tables III and IV, it will be noted that compounds through 40c were obtained by the use of ethylene oxide, whereas 410 through 80c were obtained by the use of propylene oxide alone.

Thus, in reference to Table III it is to be noted; as follows.

The example number of each compound is indicated in the first column.

The identity of the oxyalkylation-susceptible compound, to wit, the resin condensate, is indicated in the second column.

The amount of condensate is shown in the third column.

Assuming that ethylene oxide alone is employed, as happens to be the case in Examples 10 through 40c, the amount of oxide present in the oxyalkylation derivative is 26 shown in column 4, although in the initial step since no oxide is present there is a blank.

When ethylene oxide is used exclusively the 5th column is blank.

The 6th column shows the amount of powdered caustic soda used as a catalyst, and the 7th column shows the amount of solvent employed. 7

The 8th column can be ignored where a single oxide was employed.

. column 3.

Column 11 shows the amount of ethylene oxide employed in the reaction mass at the end of the particular period.

Column 12 can be ignored insofar that no propylene oxide was employed.

Column 14 shows the amount of solvent at the end of the reaction period.

Column 15 shows the molal ratio of ethylene oxide to condensate.

Column 16 can be ignored for the reason that no propylene oxide was employed.

Referring now to Table VI. It is to be noted that the first column refers to Examples 1c, 2c, 3c, etc.

The second column gives the maximum temperature employed during the oxyalkylation step and the third column gives the maximum pressure.

The fourth column gives the time period employed.

The last three columns show solubility tests by shaking a small amount of the compound, including the solvent present, with several volumes of water, xylene and hero sene. It sometimes happens that although xylene in comparatively small amounts will dissolve in the concentrated material, when the concentrated material in turn is diluted with xylene separation takes place.

Referring to Table IV, Examples 410 through 800 are the counterparts of Examples 10 through 40c, except that the oxide employed is propylene oxide instead of ethylene oxide. The reason, as explained previously, is that four columns are blank, to Wit, columns 4, 8, 11 and 15.

Reference is now made to Table V. It is to be noted these compounds are designated by d numbers, 1d, 2d, 3d, etc., through and including 32d. They are derived, in turn, from compounds in the c series, for example, 37c, 40c, 46c, and 770. These compounds involve the use of both ethylene oxide and propylene oxide. Since compounds 1c through 40c were obtained by the use of ethylene oxide, it is obvious that those obtained from 370 and 400, involve the use of ethylene oxide first, and propylene oxide afterward. Inversely, those compounds obtained from 460 and 77c obviously come from a prior series in which propylene oxide was used first.

In the preparation of this series indicated by the small letter d, as 1d, 2d, 3d, etc., the initial c series such as 37c, 40c, 46c, and 77c, were duplicated and the oxyalkylation stopped at the point designated instead of being carried further as may havebeen the case in the original oxyalkylation step. Then oxyalkylation proceeded by using the second oxide as indicated by the previous explanation, to wit, proplyene oxide in 1d through 16d, and ethylene oxide in 17d through 32d, inclusive.

In examining the table beginning with 1d, it will be noted that the initial product, i. e., 370, consisting of the reaction product involving 12.02 pounds of the resin condensate, 30.05 pounds of ethylene oxide, 1.3 pounds of caustic soda, and 5.0 pounds of the solvent.

It is to be noted that reference to the catalyst in Table V refers to the total amount of catalyst, i. e., the catalyst 28 ethylene :oxide; or, inversely,

:27 present from the first oxyalkylation step plus added :start with,pr,opylene oxide, catalyst, if any. The same is-true inregard to the.solthen use ethylene oxide, and :then go back ato propylene oxi vent. Reference tothe solvent refers to .the'total solvent present, i. e. that from the first oxyalkylation =step;plus

if any.

de; or, one. could use -a combination. ii'lTWl'llCh 'butylcne just oxide is used along -.with either oneof-the two oxides mentioned, or a combination of both of them.

added solvent it will be noted that'the-theoretical molec- The colors of the products usually vary from a reddish amber tint to a definitely red and amber. is primarily that no ,efiort is made .to obtain colorless tially and the resins .themse amber, or even dark .amber.

In thisseries, ular Weights are given prior to The reason the o-xyalkylation step and although the value at the after the 'oxyalkylation step,

lves may be yellow,

end of one step is the value at the beginning ottthe next resins ini step, except obviously-at the ve Condensation of a nitrogry-start the value depends 1r ht at the Glidof the kylation step; i. e., oxyethylation for enous product invariably yields a darker product than ddish color. .it xylene, adds nothing to the color on the theoreticalmolecular weig initial oxyal The ,and oxypropylation for 17d through 32d. t will be noted also that under the molal ratio the ues ot-hoth oxides-to the resin condensate are included. The dataigiven inregardto the ope through 16d er colored .aromatic petroleum a de lPa mmm

el u mwb generally tends to yield lighter ore oxideemployedthe lighter solvent. Oxyalkylation val colored products and the m the color of the product. Products can be prepared in which the final color is a lighter amber with a reddish tint.

Such products can be decolorized by the use of clays, ein demulsification is s v. a a .18 m a nn r c u a m m c u a 1 V is substantially-the same as'betore and VI.

The products resultingfrom these p contain modest amounts, or have sin of 24) bleaching chars, etc. As far as us all amounts, the solvents as indicated by the figures in the tables.

concerned, or someother industrial uses, there is no justification 'forthecost of bleaching the product.

desired the solventmay beremoved by distillation, and

particularly vacuum distillation. Such distillation also Generally speaking, the amount of alkaline catalyst pre ed not be re- Since the products per so are alkaline due to the iove traces "or small amounts of 'uncombined tile under the conditions em- 2.5 moved.

sent is comparatively small and it no may ren side, if present and vola ployed.

presence of a basic nitrogen, the removal of the alkaline is somewhat more difficult than ordinarily is the the reason that if one adds hydrochloric acid, for

Obviously, in the use of ethylene oxide and propylene catalyst oxide in comb ination-one need not first use oneoxide case for kalinity one may partially dicalalso. The preferred roce'dureis to ignore the presence ofthe alkal example, to neutralize the al neutralize the basic nitrogen ra "p i unless it" is objectionable or-else add a'stoichiometric amount of Needless to say, one could start with ethylene oxide concentrated hydrochloric acid equal to the caustic soda and then use propylene oxide, and then :go back to Composition at end Molal ratio Propl. oxide sate Ethyl. oxide condencondensate Solvent, lbs

' .to resin to resin Cata- .lyst, lbs

Propl oxide, lbs

Ethyl oxide,

. lbs

Theo. mol'. Wt.

present.

TABLE III Composition before Theo. mol.

Solvent, lbs

Catalyst, lbs.

oxide, lbs

Ethyl. Prop].

oxide, lbs.

0 O ii cm pd, lbs

Ex. No.

"* Oxyalkylatiomsusceptible.

TABLE VI fiq h l y EL Max. Max. Time,

Y temp, .pres,

I\o S1 1118.

' Water Xylene Kerosene amour ems: {5 A%\ KIN Soluble. Do.

Insoluble.

Soluble Do. Do.

o. Dispersible. D0

'Dispenible. Insolusble.

.32 TABLE III-Continued Ex Max Max Time Solubility temp., pres No. 0 G S 1 .1118.

' Water Xylene Kerosene 25d.130-135 20-25 Insoluble ,Soluble Insoluble. 26d- -135 20-25 1 7 do .do Do. 27d. 130-135 20-25 1% Emulsifiable Do. 28d 130-135 20-25 2% do.. Do. 29d- 130-135 20-25 1 0.. D0. 30d- 130-135 20-25 1% Soluble. D0. 31d 130-135 20-25 2 do.. W Do. 32(L 130-135 20-25 2% d0 d0 Do.

PART 5 The products described in Part 4 have utility in at least two distinct ways-the products as such .orin the form of some simple derivative, such as-the salt, which can be used in numerous arts subsequently described. Also, the products can serve as initialrnaterials for more complicated reactions of the kind ordinarily involving a hydroxyl radical. This includes esterification, etherization, etc. Likewise, the group including the nitrogen atom can be reacted with suitable reactants such as chloroacetic acid esters, benzyl chloride, alkyl halides, esters of sulfonic acids, methyl sulfate, orthe like, so as to give new ammonium compounds which may be used, not onlyfor the purpose herein described, but also for various other uses.

The products herein described as such and prepared in accordance with this invention can be used as emulsifying agents, for oils, .fats, and waxes, asingredients in insecticide compositions, or as detergents and wetting agents in the laundering, scouring, dyeing, tanning and mordanting industries. They may also be used for preparing boring or metal-cutting oils and cattle dips, as metal pickling inhibitors, and forpharmaceutical purposes.

Other uses include the preparation or resolution of petroleum emulsions, whether of the water-in-oiltype or oil-in-water type. They may be used as additives in connection with other emulsifying agents; they may be employed to contributehydrotropic efiects; they may be used as anti-strippers inconnection with asphalts; they may be used to prevent corrosiomparticularlythe corrosion of ferrous metals for various purposesand particularly in connection with the production of oil andgas, and also in refineries where crude oil is converted into various commercial products. The products may be used industrially to inhibit or stop microorganic growth or other objectionable lower forms of life, such as the growth of algae, or the like; they may be used to inhibit the growth of bacteria, molds, etc.; they are valuable additives to lubricating oils, both those derived from petroleum and syntheticlubricating oils, and also to hydraulic brake fluids of the aqueous or nonaqueous type. Some have definite anti-corrosive action;-they-rnay be used in connection with other processes where they are injected into an oil or gas well for purpose of removing a mud sheath,

for increasing the ultimate flow of fluid from the surrounding strata, and particularly in secondary recovery operations using aqueous flood waters; and for use-in dry cleaners soaps.

With regard to the above statements, reference is made particularly to the use of the materials as such, or in the form of a salt; the salt form refers to a salt involving either one or more basic nitrogen atoms. Obviously, the salt form involves a modification inwhich the hydrophile character can eitherbe increasedor decreased and,. inversely, the hydrophobe character can be decreased 0r increased. For example, neutralizing the product with practically any low molal acid, such-asacetioacid, hy-

droxy acetic acid, lactic acid, or nitric acid, is apt to in which R is a comparatively small alkyl radical, such as methyl, ethyl or propyl. The hydrophile effect may be decreased and the hydrophobe effect increased by neutralization with a monocarboxy detergent-forming acid. These are acids which have at least 8 and not more than 32 carbon atoms. They are obtained from higher fatty acids and include also resin acids such as abietic acid, and petroleum acids such as naphthenic acids and acids obtained by the oxidation of wax. One can also obtain new products having unique properties by combination with polybasic acids, such as diglycolic acid, oxalic acid, dimerized acids from linseed oil, etc. The mostcommon examples, of course, are the higher fatty acids having generally 10 to 18 carbon atoms. 1 have found that a particularly valuable anti-corrosive agent can be obtained from any suitable resin and formaldehyde provided the polyarnine includes a cyclohexyl radical. The corrosioninhibiting properties of this compound can be increased by neutralization with either one or two moles of an oilsoluble sulfonic acid, particularly a sulfonic acid of the type known as mahogany sulfonic acid.

The oil-soluble sulfonic acids previously referred to may be synthetically derived by sulfonating olefins, aliphatic fatty acids, or their esters, alkylated aromatics or their hydroxyl derivatives, partially hydrogenated aromatics, etc, with sulfuric acid or other sulfonating agents. However, the soaps of so-called mahogany acids which are usually produced during treatment of lubricating oil distillates with concentrated sulfuric acid (85% or higher concentration) remain in the oil. after settling out sludge. These sulfonic acids may be represented as a sot-n where R is one or more alkyl, alkaryl or aralkyl groups and the aromatic nucleus may be a single or condensed ring or a partially hydrogenated ring. The lower molecular weight acids can be extracted from the acid-treated oil by adding a small amount of water, preferably after dilution of the oil with kerosene. However, the more desirable high molecular weight (350400) acids, particularly those produced when treating petroleum distillates with fuming acid to produce white oil, are normally recovered as sodium soaps by neutralizing the acid oil with sodium hydroxide or carbonate and extracting with aqueous alcohol. The crude soap extract is first recovered as a water curd after removal of alcohol by distillation and a gravity separation of some of the contaminating salts (sodium carbonate, sulfates and sulfites). These materials still contain considerable quantities of salts and consequently are normally purified by addition of a more concentrated alcohol followed by storage to permit settling of salt brine. The alcohol and water are then stripped out and the sodium salts so obtained converted into free acids.

Not only can one obtain by-product sulfonic acids of the mahogany type which are perfectly satisfactory and within the molecular range of 300 to 600 but also one can obtain somewhat similar materials which are obtained as the principal product of reaction and have all the usual characteristics of normal by-product sulfonic acids but in some instances contain two sulfonic groups, i. e., are disulfonic acids. This type of mahogany acid or, better still, oil-soluble sulfonic acid, is perfectly satisfactory for the above described purpose.

Much of what has been said previously is concerned with derivatives in which the hydrophile properties are enhanced in comparison with the resin as such. A procedure designed primarily to enhance the hydrophobe properties of the resin involves derivatives obtained by a phenyl or substituted phenyl glycidyl ether of the structure in which R represents a hydrocarbon substituent such as an alkyl radical having 1 to 24 carbon atoms, or a cyclic group, such as a cyclohexyl group, a phenyl group, or a benzyl group, and n represents 0, 1, 2 or 3. n is zero in the instance of the unsubstituted phenyl radical. Such compounds are in essence oxyalkylating agents and reaction involves the introduction of a hydrophobe group and the formation of an alkanol hydroxyl radical.

The compounds herein described and particularly those adapted for breaking petroleum emulsions, although having other uses as herein noted, are derived from resins in which the bridge between phenolic nuclei is a methylene group or a substituted methylene group.

Comparable amine-modified compounds serving all these various purposes are obtainable from another class of resins, i. e., those in which the phenolic nuclei are separated by a radical having at least a 3-carbon atom chain and are obtained, not by the use of a single aldheyde but by the use of formaldehyde, in combination with a carbonyl compound selected from the class of aldehydes and ketones in which there is an. alpha hydrogen atom available as in the case of acetaldehyde or acetone. Such resins almost invariably involve the use of av basic catalyst. Such bridge radicals between phenolic nuclei have either hydroxylradicals or carbonyl radicals, or both, and are invariably oxyalkylatiomsusceptible and may also enter into more complicated reactants with basic secondary amines. The bridge radical inthe initial resin has distinct hydrophile character. Such. resins or compounds which can be converted. readily into such resins are described in. the following patents. Such analogous compounds are not included as part of the instant invention.

U. S. Patent Nos. 2,191,802, dated February 27, 1940, to Novotny et al.; 2,448,664, dated September 27, 1948, to Fife et al.; 2,538,883, dated January 23, 1951, to Schrimpe; 2,538,884, dated January 23, 1951, to Schrimpe; 2,538,559, dated March 20, 1951, to Schrimpe; 2,570,389, dated October 9, 1951, to Schrimpe.

See my co-pending applications, Serial Nos. 301,803, 301,804, 301,805, and 301,807, all filed July 30, 1952.

Having thus described my invention, what I claim as new and desire to secure by Letters Patent. is:

1. The process of first condensing (a) an oxyalkylationsusceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin hav ing an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylolform ing reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of phenols of functionality greater than 2; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms which is substituted in one of the 2, 4, and 6-positions of the phenolic nucleus; (b) a basic hydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical, and any substituted tetrahydropyrirnidine radical; and (0) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; the molar ratio of the reactants a, b and c being approximately 1:222, respectively and with the proviso that the resinous condensation product resulting from the process be heatstable and oxyalkylation-susceptible; thereafter oxyalkylating the resulting condensation product by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

2. The process of first condensing (a) an oxyethy1ationsusceptible, fusible, non-oxygenated organic solventsoluble, Water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nucei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of phenols of functionality greater than 2; said phenol being of the formula tion reaction being conducted at a temperature sulficiently.

high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the added proviso that the ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; thereafter oxyalkylating said condensation product by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

3. The process of claim 1 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination.

4. The process of claim 2 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination.

5. The product resulting from the process defined in claim 1.

6. The product resulting from the process defined in claim 2.

7. The product resulting from the process defined in claim 3.

8. The product resulting from the process defined in claim 4.

References Cited in the file of this patent UNITED STATES PATENTS 

1. THE PROCESS OF FIRST CONDENSING (A) ORGANIC SOLVENT-SOLUSUSCEPTIBLE, FUSIBLE, NON-OXYGENATED ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE, LOW-STAGE PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOL-FORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF PHENOLS OF FUNCTIONALITY GREATER THAN 2; SAID PHENOL BEING OF THE FORMULA 